U.S. patent application number 11/121742 was filed with the patent office on 2005-11-10 for fluoropolyether poly(meth)acryl compounds.
This patent application is currently assigned to 3M Innovative Properties Company. Invention is credited to Chang, John C., Elsbernd, Cheryl L. S., Guerra, Miguel A., Jing, Naiyong, Klun, Thomas P., Moore, George G. I., Qiu, Zai-Ming.
Application Number | 20050249940 11/121742 |
Document ID | / |
Family ID | 46123895 |
Filed Date | 2005-11-10 |
United States Patent
Application |
20050249940 |
Kind Code |
A1 |
Klun, Thomas P. ; et
al. |
November 10, 2005 |
Fluoropolyether poly(meth)acryl compounds
Abstract
Fluoropolyether poly(meth)acryl compounds comprising at least
one terminal perfluoropolyether group and at least two groups
(meth)acryl groups. A preferred perfluoropolyether group includes
F(CF(CF.sub.3)CF.sub.2O).sub.- aCF(CF.sub.3)-- group wherein a
averages 1 to 15 and at least two groups (meth)acryl groups.
Inventors: |
Klun, Thomas P.; (Lakeland,
MN) ; Chang, John C.; (New Brighton, MN) ;
Elsbernd, Cheryl L. S.; (Woodbury, MN) ; Guerra,
Miguel A.; (Woodbury, MN) ; Jing, Naiyong;
(Woodbury, MN) ; Moore, George G. I.; (Afton,
MN) ; Qiu, Zai-Ming; (Woodbury, MN) |
Correspondence
Address: |
3M INNOVATIVE PROPERTIES COMPANY
PO BOX 33427
ST. PAUL
MN
55133-3427
US
|
Assignee: |
3M Innovative Properties
Company
|
Family ID: |
46123895 |
Appl. No.: |
11/121742 |
Filed: |
May 4, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11121742 |
May 4, 2005 |
|
|
|
11026700 |
Dec 30, 2004 |
|
|
|
60569351 |
May 7, 2004 |
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Current U.S.
Class: |
428/323 ;
428/421; 428/422 |
Current CPC
Class: |
B32B 5/16 20130101; Y10T
428/3154 20150401; Y10T 428/25 20150115; C08G 65/226 20130101; Y10T
428/31544 20150401; C08G 65/3322 20130101; B32B 27/00 20130101;
C08G 65/331 20130101; C08L 1/00 20130101 |
Class at
Publication: |
428/323 ;
428/421; 428/422 |
International
Class: |
B32B 005/16; B32B
027/00 |
Claims
What is claimed is:
1. A fluoropolyether poly(meth)acryl compound comprising at least
one terminal perfluoropolyether group and at least two groups
(meth)acryl groups.
2. The fluoropolyether poly(meth)acryl compound of claim 1 wherein
the perfluoropolyether group is
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- wherein a averages 1
to 15.
3. A fluoropolyether poly(meth)acryl compound of claim 2 wherein a
averages between 3 and 10.
4. The fluoropolyether poly(meth)acryl compound of claim 2 wherein
a averages 5 to 8.
5. The fluoropolyether poly(meth)acryl compound of claim 1 wherein
the (meth)acryl groups are independently selected from methacrylate
groups and acrylate groups.
6. The fluoropolyether poly(meth)acryl compound of claim 1 wherein
the compound is of the formula (R.sub.fpe).sub.nQ(X).sub.m wherein:
R.sub.fpe is the residue of a monovalent HFPO moiety of the formula
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- where a is 3 to 15 and
n is 1 to 3; Q is a connecting group of valency at least 2 and is
selected from the group consisting of a covalent bond, an alkylene,
an arylene, an aralkylene, an alkarylene, a straight or branched
chain or cycle-containing connecting group optionally containing
heteroatoms O, N, and S and optionally a heteroatom-containing
functional group such as carbonyl or sulfonyl, and combinations
thereof; X is a (meth)acryl functional group -AC(O)C(R)=CH.sub.2,
where A is O, S or NR.sub.1, R is a lower alkyl of 1 to 4 carbon
atoms or H or F, R.sub.1 is H or lower alkyl of 1 to 4 carbon
atoms, and m is 2-10.
7. The fluoropolyether poly(meth)acryl compound of claim 1 wherein
the compound is of the formula
B--O(CH.sub.2CH(OB)CH.sub.2O).sub.nCH.sub.2CH(- OB)CH.sub.2O--B
wherein n ranges from 0 to 20, and B is independently H,
--C(O)CH.dbd.CH.sub.2, or --C(O)--HFPO, and in which at least one B
is --C(O)--HFPO and at least two B are --C(O)CH.dbd.CH.sub.2.
8. The fluoropolyether poly(meth)acryl compound of claim 1 wherein
the compound is reaction product of the reaction 7wherein R.sub.2
is hydrogen, alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl,
HFPO--C(O)--, R.sub.3 is independently H or
CH.sub.2.dbd.C(CH.sub.3)C(O)-- -OC.sub.2H.sub.4NHC(O)--, R.sub.4 is
alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl,
HFPO--C(O)--, or CH.sub.2.dbd.C(CH.sub.3)C(O)--OC.sub-
.2H.sub.4NHC(O)--, R.sub.5 is alkyl, aryl, arylalkyl, alkylaryl,
fluoroalkyl, acryl, HFPO--C(O)--, or
CH.sub.2.dbd.C(CH.sub.3)C(O)--OCH.su- b.2CH(OH)CH.sub.2--, R.sub.6
is independently H or CH.sub.2.dbd.C(CH.sub.3-
)C(O)--OCH.sub.2CH(OH)CH.sub.2--, and n ranges from an average
about 2 to 32.
9. The fluoropolyether poly(meth)acryl compound of claim 1 wherein
the compound is selected from the group consisting of a)
HFPO--C(O)NHC(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.3; b)
HFPO--C(O)N(CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2; c)
HFPO--C(O)NHCH.sub.2CH.sub.2N(C(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)CH.dbd.CH.-
sub.2; d) HFPO--C(O)NHC(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2H; e)
HFPO--C(O)NHC(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2CH.sub.3; f)
HFPO--C(O)NH(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2CH.sub.2CH.sub.3;
g)
HFPO--C(O)NHCH.sub.2CH(OC(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)CH.dbd.CH.sub.2;
h)
HFPO--C(O)NHCH.sub.2CH.sub.2CH.sub.2N(CH.sub.2CH.sub.2OC(O)CH.dbd.CH.s-
ub.2).sub.2; i)
HFPO--C(O)OCH.sub.2C(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.3; j)
HFPO--C(O)NH(CH.sub.2CH.sub.2N(C(O)CH.dbd.CH.sub.2)).sub.4CH.sub.2CH.s-
ub.2NC(O)--HFPO; k)
CH.sub.2.dbd.CHC(O)OCH.sub.2CH(OC(O)HFPO)CH.sub.2OCH.s-
ub.2CH(OH)CH.sub.2OCH.sub.2CH(OC(O)HFPO)CH.sub.2OCOCH.dbd.CH.sub.2;
and l)
HFPO--CH.sub.2O--CH.sub.2CH(OC(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)CH.dbd.CH.s-
ub.2.
10. An article comprising a substrate and a surface layer
comprising the fluoropolyether poly(meth)acryl compound of claim
1.
11. The article of claim 10 wherein the surface layer comprises the
reaction product of a polymerizable composition comprising the
fluoropolyether poly(meth)acryl compound of claim 1.
12. A coating composition comprising at least one fluoropolyether
poly(meth)acryl compound of claim 1 and a diluent selected from
solvent, (meth)acryl monomer, and mixtures thereof.
13. The coating composition of claim 12 wherein the amount of
fluoropolyether poly(meth)acryl compound ranges from to 0.05 wt-%
solids to 15 wt-% solids.
14. The coating composition of claim 12 wherein the solvent is
selected from non-fluorinated organic solvents, fluorinated organic
solvents, and mixtures thereof.
15. The coating composition of claim 12 wherein the composition
further comprises a second fluorinated compound.
16. The coating composition of claim 15 wherein the second
fluorinated compound is a fluoropolyether acrylate.
17. The coating composition of claim 12 further comprising a
poly(meth)acryl crosslinking agent.
18. The coating composition of claim 17 wherein the crosslinking
agent is non-fluorinated.
19. The coating composition of claim 11 wherein the dried and
optionally cured coating composition exhibits ink repellency.
20. A ceramer comprising a binder, inorganic particles, and the
fluoropolyether poly(meth)acryl compound of claim 1.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent
Application No. 60/569,351, filed May 7, 2004, and is a
continuation-in-part of U.S. patent application Ser. No. 11/026700,
filed Dec. 30, 2004.
SUMMARY OF THE INVENTION
[0002] Fluoropolyether poly(meth)acryl compound are described that
comprise at least one terminal perfluoropolyether group, such as
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- wherein a averages 1
to 15, and at least two groups (meth)acryl groups. In some
embodiments, a averages between 3 and 10 or a averages between 5
and 8. The (meth)acryl groups may be independently selected from
methacrylate groups and acrylate groups.
[0003] In another embodiment, the invention relates to a substrate
and a surface layer disposed on the substrate wherein the surface
layer comprises at least one of the described fluoropolyether
poly(meth)acryl compounds. The surface layer may comprise the
reaction product of a polymerizable composition comprising the
described fluoropolyether poly(meth)acryl compounds.
[0004] In another embodiment, the invention relates to a coating
composition comprising the fluoropolyether poly(meth)acryl compound
and a diluent such as a solvent, a (meth)acryl monomer, and
mixtures thereof. The solvent may include non-fluorinated organic
solvents, fluorinated organic solvents, and mixtures thereof.
[0005] In another embodiment, the invention relates to a ceramer
comprising a binder, inorganic particles, and the fluoropolyether
poly(meth)acryl compound.
[0006] The amount of fluoropolyether poly(meth)acryl compound in
the surface layer, coating, or ceramer may range from 0.05 wt-% to
15 wt-%.
[0007] The dried and optionally cured surface layer exhibits ink
repellency and is preferably durable.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0008] The present invention describes compounds having at least
one fluoropolyether group and at least two (meth)acryl groups.
[0009] The fluoropolyether group preferably comprises
perfluorinated propylene oxide repeat units. More preferably, the
compound comprises at least one terminal
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- group wherein "a"
averages at least about 3 (e.g. 4, 5). Further, "a" typically
averages no more than 15 (e.g. 14, 13, 12, 11, 10, 9, or 8). In
some aspects, "a" averages 6 to 7. Unless stated otherwise, as used
in the detailed description, "HFPO-" refers to the end group
wherein a averages about 3 to 15.
[0010] The compound of the invention comprises at least two
(meth)acryl groups. The (meth)acryl groups are preferably
(meth)acrylate groups optionally substituted with hydrogen and/or
fluorine. In at least some embodiments, the (meth)acryl groups are
preferably acrylate groups.
[0011] The fluoropolyether poly(meth)acryl compounds described
herein may have the formula (R.sub.fpe).sub.nQ(X).sub.m
wherein:
[0012] R.sub.fpe is the residue of a monovalent HFPO moiety of the
formula F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- wherein a is 3
to 15 and n is 1 to 3;
[0013] Q is a connecting group of valency at least 2 and is
selected from the group consisting of a covalent bond, an alkylene,
an arylene, an aralkylene, an alkarylene, a straight or branched
chain or cycle-containing connecting group optionally containing
heteroatoms O, N, and S and optionally a heteroatom-containing
functional group such as carbonyl or sulfonyl, and combinations
thereof;
[0014] X is a (meth)acryl functional group-AC(O)C(R)=CH.sub.2,
wherein A is O, S or NR.sub.1, R is a lower alkyl of 1 to 4 carbon
atoms or H or F, R.sub.1 is H or lower alkyl of 1 to 4 carbon
atoms, and m is 2-10.
[0015] Exemplary compounds include for example:
[0016] a) HFPO--C(O)NHC(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.3
[0017] b)
HFPO--C(O)N(CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2
[0018] c)
HFPO--C(O)NHCH.sub.2CH.sub.2N(C(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)C-
H.dbd.CH.sub.2
[0019] d) HFPO--C(O)NHC(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2H
[0020] e)
HFPO--C(O)NHC(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2CH.sub.3
[0021] f)
HFPO--C(O)NHC(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2CH.sub.2CH.sub.-
3
[0022] g)
HFPO--C(O)NHCH.sub.2CH(OC(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)CH.dbd.-
CH.sub.2
[0023] h)
HFPO--C(O)NHCH.sub.2CH.sub.2CH.sub.2N(CH.sub.2CH.sub.2OC(O)CH.db-
d.CH.sub.2).sub.2
[0024] i)
HFPO--C(O)OCH.sub.2C(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.3
[0025] j)
HFPO--C(O)NH(CH.sub.2CH.sub.2N(C(O)CH.dbd.CH.sub.2)).sub.4CH.sub-
.2CH.sub.2NC(O)--HFPO
[0026] k)
CH.sub.2.dbd.CHC(O)OCH.sub.2CH(OC(O)HFPO)CH.sub.2OCH.sub.2CH(OH)-
CH.sub.2OCH.sub.2CH(OC(O)HFPO)CH .sub.2OCOCH.dbd.CH.sub.2; and
[0027] l)
HFPO--CH.sub.2O--CH.sub.2CH(OC(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)CH-
.dbd.CH.sub.2
[0028] The fluoropolyether poly(meth)acryl compounds described
herein may have the formula
B--O(CH.sub.2CH(OB)CH.sub.2O).sub.nCH.sub.2CH(OB)CH.sub.- 2O--B
wherein n ranges from 0 to 20, and B is independently H,
--C(O)CH.dbd.CH.sub.2, or --C(O)--HFPO, and in which at least one B
is --C(O)--HFPO and at least two B's are --C(O)CH.dbd.CH.sub.2.
[0029] An exemplary compound of this type is
CH.sub.2.dbd.CHC(O)OCH.sub.2C-
H(OC(O)HFPO)CH.sub.2OCH.sub.2CH(OH)CH.sub.2OCH.sub.2CH(OC(O)HFPO)CH
.sub.2OC(O)CH.dbd.CH.sub.2.
[0030] The fluoropolyether poly(meth)acryl compounds may be the
reaction product of either of the following Reaction Sequences A
and B: 1 2
[0031] In each of Reaction Sequences A and B, R.sub.2 is hydrogen,
alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl,
HFPO--C(O)--, R.sub.3 is independently H or
CH.sub.2.dbd.C(CH.sub.3)C(O)--OC.sub.2H.sub.4NHC(O)--, R.sub.4 is
alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl,
HFPO--C(O)--, or
CH.sub.2.dbd.C(CH.sub.3)C(O)--OC.sub.2H.sub.4NHC(O)--, R.sub.5 is
alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl,
HFPO--C(O)--, or
CH.sub.2.dbd.C(CH.sub.3)C(O)--OCH.sub.2CH(OH)CH.sub.2--, R.sub.6 is
independently H or CH.sub.2.dbd.C(CH.sub.3)C(O)--OCH.sub.2CH(O-
H)CH.sub.2--, and n ranges from an average about 2 to 32.
[0032] The fluoropolyether poly(meth)acryl compounds described
herein can be prepared in a two step process. The first step is by
reaction of poly(hexafluoropropylene oxide) esters, such as
HFPO--C(O)OCH.sub.3 or acid halides HFPO--C(O)F, with materials
containing at least 3 alcohol or primary or secondary amino groups
to produce HFPO-- amide polyols or polyamines, HFPO-- ester polyols
or polyamines, or HFPO-- amides, or HFPO-- esters with mixed amine
and alcohol groups. The second step is the (meth)acrylation of the
alcohol and/or amine groups with (meth)acryloyl halides,
(meth)acrylic anhydrides or (meth)acrylic acid. Exemplary syntheses
thereof are set forth in the examples.
[0033] The fluoropolyether poly(meth)acryl compounds can be
employed as a surface layer on a variety of articles in order to
impart low surface energy properties.
[0034] The surface energy can be characterized by various methods
such as contact angle and ink repellency, as determined according
to the test methods described in the examples. The surface layer
and articles described herein preferably exhibits a static contact
angle with water of at least 70.degree.. More preferably the
contact angle with water is at least 80.degree. and even more
preferably at least 90.degree. (e.g. at least 95.degree., at least
100.degree.). Alternatively or in addition thereto, the advancing
contact angle with hexadecane is at least 50.degree. and more
preferably at least 600. Low surface energy is indicative of
anti-soiling properties as well as the surface being easy to clean.
As yet another indication of low surface energy, ink from a marker
commercially available under the trade designation "Sanford
Sharpie, Fine Point permanent marker, no 30001" preferably beads
up. Further, the surface layer and articles described herein
exhibit "ink repellency", meaning that the ink can easily be
removed by wiping with a tissue commercially available from
Kimberly Clark Corporation, Roswell, Ga. under the trade
designation "SURPASS FACIAL TISSUE".
[0035] As used herein, wt-% refers to wt-% solids unless indicated
otherwise such as in the case of non-polymerizable diluent.
[0036] The fluorochemical surface layer comprises at least one of
the fluoropolyether poly(meth)acryl compounds described herein,
optionally in combination with other polymerizable ingredients
(e.g. (meth)acryl monomers and/or crosslinkers) and/or a solvent.
The total amount of fluoropolyether poly(meth)acryl compound in the
coating composition that is polymerized to form the surface layer
is typically at least 0.05 wt-% solids (e.g. at least about 0.10
wt-%, 0.50 wt-%, 1 wt-%, 2 wt-%, 3 wt-%, and 4 wt-%). In some
embodiments, the coating composition comprises at least about 5
wt-% solids fluoropolyether poly(meth)acryl compounds. In other
embodiments, such as when the fluoropolyether poly(meth)acryl
compound of the invention is added to a hardcoat, the hardcoat
composition may contain as little as 0.1 wt-% or lower amounts of
the fluoropolyether poly(meth)acryl compound(s).
[0037] The coating composition may contain as much as 95 wt-%
solids of one or more of the described fluoropolyether
poly(meth)acryl compounds. It is generally more cost effective to
employ a minimal concentration of fluorinated compound that provide
the desired low surface energy. Accordingly, the total amount of
fluoropolyether poly(meth)acryl compound(s) provided in the coating
composition typically does not exceed 30 wt-% and usually is
present is an amount of no more than about 15 wt-% (e.g. less than
about 14 wt-%, 13 wt-%, 12 wt-%, and 11 wt-%).
[0038] In some aspects, the reaction product of a polymerizable
composition comprising the fluoropolyther poly(meth)acryl compounds
of the invention can be employed as a surface layer optionally
above an underlying hardcoat layer, such as described in for
example Liu et al., U.S. Pat. No. 6,660,389. The polymerizable
composition typically further comprise one or more (e.g.
non-fluorinated) (meth)acryl monomers, (meth)acryl oligomers, or
(meth)acryl polymers. In order to improve the durability of the
surface layer, the reaction product may further comprise at least
one crosslinking agent. "Crosslinking agent" and "crosslinker" are
used herein interchangeably and refer to a monomer or oligomer
having at least two (meth)acryl groups. Preferably, the crosslinker
comprises at least two (meth)acrylate groups and thus is a
poly(meth)acrylate compound. In at least some embodiments, acrylate
groups are preferred.
[0039] Although fluorinated crosslinkers can be employed, it is
generally more cost effective to utilize non-fluorinated
crosslinking agents. As little as 5 wt-% crosslinker can result in
suitable durability for some applications. However, it is typical
to maximize the concentration of crosslinker particularly since
non-fluorinated (meth)acrylate crosslinkers are generally less
expensive than fluorinated compounds. Accordingly, the coating
compositions described herein typically comprise at least 20 wt-%
crosslinking agent(s). The total amount of crosslinking agent(s)
may comprise at least 50 wt-% and may be for example at least 60
wt-%, at least 70 wt-%, at least 80 wt-%, at least 90 wt-% and even
about 95 wt-% or greater of the coating composition.
[0040] Useful crosslinking agents include, for example,
poly(meth)acryl monomers selected from the group consisting of (a)
di(meth)acryl containing compounds such as 1,3-butylene glycol
diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,
1,6-hexanediol monoacrylate monomethacrylate, ethylene glycol
diacrylate, alkoxylated aliphatic diacrylate, alkoxylated
cyclohexane dimethanol diacrylate, alkoxylated hexanediol
diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone
modified neopentylglycol hydroxypivalate diacrylate, caprolactone
modified neopentylglycol hydroxypivalate diacrylate,
cyclohexanedimethanol diacrylate, diethylene glycol diacrylate,
dipropylene glycol diacrylate, ethoxylated (10) bisphenol A
diacrylate, ethoxylated (3) bisphenol A diacrylate, ethoxylated
(30) bisphenol A diacrylate, ethoxylated (4) bisphenol A
diacrylate, hydroxypivalaldehyde modified trimethylolpropane
diacrylate, neopentyl glycol diacrylate, polyethylene glycol (200)
diacrylate, polyethylene glycol (400) diacrylate, polyethylene
glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate,
tetraethylene glycol diacrylate, tricyclodecanedimethanol
diacrylate, triethylene glycol diacrylate, tripropylene glycol
diacrylate; (b) tri(meth)acryl containing compounds such as
glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated
triacrylates (e.g., ethoxylated (3) trimethylolpropane triacrylate,
ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9)
trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropane
triacrylate), pentaerythritol triacrylate, propoxylated
triacrylates (e.g., propoxylated (3) glyceryl triacrylate,
propoxylated (5.5) glyceryl triacrylate, propoxylated (3)
trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane
triacrylate), trimethylolpropane triacrylate,
tris(2-hydroxyethyl)isocyanurate triacrylate; (c) higher
functionality (meth)acryl containing compounds such as
ditrimethylolpropane tetraacrylate, dipentaerythritol
pentaacrylate, ethoxylated (4) pentaerythritol tetraacrylate,
pentaerythritol tetraacrylate, caprolactone modified
dipentaerythritol hexaacrylate; (d) oligomeric (meth)acryl
compounds such as, for example, urethane acrylates, polyester
acrylates, epoxy acrylates; polyacrylamide analogues of the
foregoing; and combinations thereof. Such compounds are widely
available from vendors such as, for example, Sartomer Company,
Exton, Pa.; UCB Chemicals Corporation, Smyrna, Ga.; and Aldrich
Chemical Company, Milwaukee, Wis. Additional useful (meth)acrylate
materials include hydantoin moiety-containing poly(meth)acrylates,
for example, as described in U.S. Pat. No. 4,262,072 (Wendling et
al.).
[0041] A preferred crosslinking agent comprises at least three
(meth)acrylate functional groups. Commercially available
crosslinking agent include those available from Sartomer Company,
Exton, Pa. such as trimethylolpropane triacrylate available under
the trade designation "SR351", pentaerythritol triacrylate
available under the trade designation "SR444", dipentaerythritol
pentaacrylate available under the trade designation "SR399LV",
ethoxylated (3) trimethylolpropane triacrylate available under the
trade designation "SR454", and ethoxylated (4) pentaerythritol
triacrylate, available under the trade designation "SR494".
[0042] The coating composition described herein may comprise
various combinations of one or more of the (per)fluoropolyether
poly(meth)acryl compound of the invention. Further, the inventive
compounds may be employed in combination with other known
monofunctional (per)fluoropolyether compound(s) and polyfunctional
(per)fluoropolyether compounds.
[0043] Alternatively or in addition thereto, the coating
composition described herein may further various other reactive and
non-reactive ingredients. For example the composition may comprise
polymerizable (meth)acryl compounds with alkyl, perfluoroalkyl, and
perfluoroalkylene moieties. Examples of these compounds include
butyl acrylate, 1H,1H-2,2,3,3,4,4,4-heptafluorobutyl acrylate,
available from Sigma-Aldrich; 1H,1H,2H,2H-perfluorodecyl acrylate,
available from Lancaster Synthesis, Windham, N.H.; and
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)-
CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2 made by the procedure of
Examples 2A and 2B of WO01/30873A. Other (meth)acryl compounds with
perfluoroalkyl moieties are mentioned in U.S. Pat. No. 4,968,116
and in U.S. Pat. No. 5,239,026 (including
(perfluorocyclohexyl)methyl acrylate).
[0044] To facilitate curing, polymerizable compositions according
to the present invention may further comprise at least one
free-radical thermal initiator and/or photoinitiator. Typically, if
such an initiator and/or photoinitiator are present, it comprises
less than about 10 percent by weight, more typically less than
about 5 percent of the polymerizable composition, based on the
total weight of the polymerizable composition. Free-radical curing
techniques are well known in the art and include, for example,
thermal curing methods as well as radiation curing methods such as
electron beam or ultraviolet radiation. Further details concerning
free radical thermal and photopolymerization techniques may be
found in, for example, U.S. Pat. Nos. 4,654,233 (Grant et al.);
4,855,184 (Klun et al.); and 6,224,949 (Wright et al.).
[0045] Useful free-radical thermal initiators include, for example,
azo, peroxide, persulfate, and redox initiators, and combinations
thereof.
[0046] Useful free-radical photoinitiators include, for example,
those known as useful in the UV cure of acrylate polymers. Such
initiators include benzophenone and its derivatives; benzoin,
alpha-methylbenzoin, alpha-phenylbenzoin, alpha-allylbenzoin,
alpha-benzylbenzoin; benzoin ethers such as benzil dimethyl ketal
(commercially available under the trade designation "IRGACURE 651"
from Ciba Specialty Chemicals Corporation of Tarrytown, N.Y.),
benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether;
acetophenone and its derivatives such as
2-hydroxy-2-methyl-1-phenyl-1-propanone (commercially available
under the trade designation "DAROCUR 1173" from Ciba Specialty
Chemicals Corporation) and 1-hydroxycyclohexyl phenyl ketone
(commercially available under the trade designation "IRGACURE 184",
also from Ciba Specialty Chemicals Corporation);
2-methyl-1-[4-(methylthio)phenyl]-2-(4-- morpholinyl)-1-propanone
commercially available under the trade designation "IRGACURE 907",
also from Ciba Specialty Chemicals Corporation);
2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-bu- tanone
commercially available under the trade designation "IRGACURE 369"
from Ciba Specialty Chemicals Corporation); aromatic ketones such
as benzophenone and its derivatives and anthraquinone and its
derivatives; onium salts such as diazonium salts, iodonium salts,
sulfonium salts; titanium complexes such as, for example, that
which is commercially available under the trade designation "CGI
784 DC", also from Ciba Specialty Chemicals Corporation);
halomethylnitrobenzenes; and mono- and bis-acylphosphines such as
those available from Ciba Specialty Chemicals Corporation under the
trade designations "IRGACURE 1700", "IRGACURE 1800", "IRGACURE
1850","IRGACURE 819" "IRGACURE 2005", "IRGACURE 2010", "IRGACURE
2020" and "DAROCUR 4265". Combinations of two or more
photoinitiators may be used. Further, sensitizers such as
2-isopropyl thioxanthone, commercially available from First
Chemical Corporation, Pascagoula, Miss., may be used in conjunction
with photoinitiator(s) such as ""IRGACURE 369".
[0047] The coating compositions can contain other optional
adjuvants, such as, surfactants, antistatic agents (e.g.,
conductive polymers), leveling agents, photosensitizers,
ultraviolet ("UV") absorbers, stabilizers, antioxidants,
lubricants, pigments, dyes, plasticizers, suspending agents and the
like.
[0048] The compositions described herein can provide a synergistic
combination of low surface energy as imparted by the
(per)fluoropolyether (meth)acryl compound in combination with good
durability, as imparted by the hydrocarbon crosslinking agent. The
composition described herein is typically free of hydrophilic
ingredients (e.g. monomers) since the inclusion of such tends to
reduce anti-soiling properties as well as stain certain media (e.g.
substrates). Hydrophilic components are also susceptible to
degradation upon exposure to aqueous based cleaning agents.
[0049] The surface layer and articles described herein are also
preferably durable, meaning that the surface exhibits substantially
no surface damage or significant loss of optical properties (e.g.
retains 97% of its original transmission) after durability testing
conducted according to the test method described in the examples
wherein cheesecloth is employed with a 725 g weight and 200 wipes.
Further, the surface layer and articles preferably continues to
exhibit the previously described low surface energy properties
(e.g. contact angles, ink repellency, and bead up) even after such
durability testing.
[0050] The presently described surface layer does not detract from
the optical qualities of the article (e.g. display). Accordingly,
the articles of the invention exhibit substantially the same
initial haze and transmission values in comparison to the same
substrate or hardcoat coated substrate lacking such surface layer
as described herein. Preferably the haze and transmission values
are substantially the same after durability testing.
[0051] The coating composition of the invention can be applied as a
separate surface layer using a diluent that assists in coating of
the composition. Those skilled in the art will appreciate that
selection of a desired diluent and diluent level will depend on the
substrate or surface being coated, the ingredients of the coating
composition, and on the coating conditions. Although fluorinated
solvents could optionally be employed alone or in combination with
an organic solvent, the (per)fluoropolyether acrylate(s) and
crosslinking agent are generally sufficiently soluble in
non-fluorinated solvent. Thus, the coating composition can
advantageously be free of fluorinated solvents. Solvents include
ketones such as methyl ethyl ketone (MEK), methyl isobutylene
ketone (MIBK), and methyl propyl ketone (MPK); and acetates such as
ethyl acetate, at a concentration to obtain the intended coating
thickness (e.g. 2% to 3% solids). Any adjuvants, as previously
described, are typically added after dissolution with the
solvent.
[0052] Alternatively, 100% solids composition can be made by use of
one or more (meth)acryl monomers as a diluent.
[0053] The coating composition can be applied to a substrate or
hardcoat layer disposed on a substrate using a variety of
conventional coating methods. Suitable coating methods include, for
example, spin coating, knife coating, die coating, wire coating,
flood coating, padding, spraying, roll coating, dipping, brushing,
foam application, and the like. The coating is dried, typically
using a forced air oven. The dried coating is at least partially
and typically completely cured using an energy source.
[0054] Energy sources include ultraviolet light curing devices that
provide a UV "C" dosage of about 5 to 60 millijoules per square
centimeter (mJ/cm.sup.2). Curing takes place in an environment
containing low amounts of oxygen, e.g., less than about 100 parts
per million. Nitrogen gas is a suitable environment.
[0055] The coating composition is applied at a sufficient amount to
provide a cured layer having a thickness of at least about 10
nanometers, and typically at least about 25 nanometers. The cured
layer may have a thickness of less than about 200 nanometers, less
than about 100 nanometers, or less than about 75 nanometers. In
such embodiments, the bulk of the durability may be provided by an
underlying hardcoat layer.
[0056] As an alternative to providing the coating of the invention
as a surface layer on an article or surface such as could be done
during the manufacture of the display panel, the coating
composition of the invention may be employed as a (e.g. surface)
layer on a protective article. For example, such protective
articles are described in U.S. Pat. No. 6,660,389; incorporated
herein by reference.
[0057] Various permanent and removable grade adhesive compositions
may be coated on the opposite side of the substrate of the
protective article (i.e. to that of the hardcoat) so the article
can be easily mounted to a display surface. Suitable adhesive
compositions include (e.g. hydrogenated) block copolymers such as
those commercially available from Kraton Polymers, Westhollow, Tex.
under the trade designation "Kraton G-1657", as well as other (e.g.
similar) thermoplastic rubbers. Other exemplary adhesives include
acrylic-based, urethane-based, silicone-based and epoxy-based
adhesives. Preferred adhesives are of sufficient optical quality
and light stability such that the adhesive does not yellow with
time or upon weather exposure so as to degrade the viewing quality
of the optical display. The adhesive can be applied using a variety
of known coating techniques such as transfer coating, knife
coating, spin coating, die coating and the like. Exemplary adhesive
are described in U.S. Patent Application Publication No.
2003/0012936. Several of such adhesives are commercially available
from 3M Company, St. Paul, Minn. under the trade designations 8141,
8142, and 8161.
[0058] A variety of substrates can be utilized in the articles of
the invention. Suitable substrate materials include glass as well
as thermosetting or thermoplastic polymers such as polycarbonate,
poly(meth)acrylate (e.g., polymethyl methacrylate or "PMMA"),
polyolefins (e.g., polypropylene or "PP"), polyurethane, polyesters
(e.g., polyethylene terephthalate or "PET"), polyamides,
polyimides, phenolic resins, cellulose diacetate, cellulose
triacetate, polystyrene, styrene-acrylonitrile copolymers, epoxies,
and the like. Typically the substrate will be chosen based in part
on the desired optical and mechanical properties for the intended
use. Such mechanical properties typically will include flexibility,
dimensional stability and impact resistance. The substrate
thickness typically also will depend on the intended use. For most
applications, substrate thicknesses of less than about 0.5 mm are
typical, and more typically the thickness ranges from about 0.02 mm
to about 0.2 mm. Self-supporting polymeric films are preferred.
Films made from polyesters such as PET or polyolefins such as PP
(polypropylene), PE (polyethylene) and PVC (polyvinyl chloride) are
particularly preferred. The polymeric material can be formed into a
film using conventional filmmaking techniques such as by extrusion
and optional uniaxial or biaxial orientation of the extruded film.
The substrate can be treated to improve adhesion between the
substrate and the hardcoat layer, e.g., chemical treatment, corona
treatment such as air or nitrogen corona, plasma, flame, or actinic
radiation. If desired, an optional tie layer or primer can be
applied to the substrate and/or hardcoat layer to increase the
interlayer adhesion.
[0059] In the case of articles such as display panels and
protective articles, the substrate is light transmissive, meaning
light can be transmitted through the substrate such that the
display can be viewed. Both transparent (e.g. gloss) and matte
light transmissive substrates are employed in display panels. Matte
substrates typically have lower transmission and higher haze values
than typical gloss films. The matte films exhibit this property
typically due to the presence of micron size dispersed inorganic
fillers such as silica that diffuse light. Exemplary matte films
are commercially available from U.S.A. Kimoto Tech, Cedartown, Ga.
under the trade designation "N4D2A". In case of transparent
substrates, hardcoat coated transparent substrates, as well as the
display articles comprised of transparent substrates, the haze
value is preferably less than 5%, more preferably less than 2% and
even more preferably less than 1%. Alternatively or in addition
thereto, the transmission is preferably greater than about 90%.
[0060] A variety of inorganic oxide particles can be used in the
hardcoat. The particles are typically substantially spherical in
shape and relatively uniform in size. The particles can have a
substantially monodisperse size distribution or a polymodal
distribution obtained by blending two or more substantially
monodisperse distributions. The inorganic oxide particles are
typically non-aggregated (substantially discrete), as aggregation
can result in precipitation of the inorganic oxide particles or
gelation of the hardcoat. The inorganic oxide particles are
typically colloidal in size, having an average particle diameter of
about 0.001 to about 0.2 micrometers, less than about 0.05
micrometers, and less than about 0.03 micrometers. These size
ranges facilitate dispersion of the inorganic oxide particles into
the binder resin and provide ceramers with desirable surface
properties and optical clarity. The average particle size of the
inorganic oxide particles can be measured using transmission
electron microscopy to count the number of inorganic oxide
particles of a given diameter. Inorganic oxide particles include
colloidal silica, colloidal titania, colloidal alumina, colloidal
zirconia, colloidal vanadia, colloidal chromia, colloidal iron
oxide, colloidal antimony oxide, colloidal tin oxide, and mixtures
thereof. The inorganic oxide particles can consist essentially of
or consist of a single oxide such as silica, or can comprise a
combination of oxides, such as silica and aluminum oxide, or a core
of an oxide of one type (or a core of a material other than a metal
oxide) on which is deposited an oxide of another type. Silica is a
common inorganic particle. The inorganic oxide particles are often
provided in the form of a sol containing a colloidal dispersion of
inorganic oxide particles in liquid media. The sol can be prepared
using a variety of techniques and in a variety of forms including
hydrosols (where water serves as the liquid medium), organosols
(where organic liquids so serve), and mixed sols (where the liquid
medium contains both water and an organic liquid), e.g., as
described in U.S. Pat. Nos. 5,648,407 (Goetz et al.); 5,677,050
(Bilkadi et al.) and 6,299,799 (Craig et al.), the disclosure of
which is incorporated by reference herein. Aqueous sols (e.g. of
amorphous silica) can be employed. Sols generally contain at least
2 wt-%, at least 10 wt-%, at least 15 wt-%, at least 25 wt-%, and
often at least 35 wt-% colloidal inorganic oxide particles based on
the total weight of the sol. The amount of colloidal inorganic
oxide particle is typically no more than 50 wt-% (e.g. 45 wt-%).
The surface of the inorganic particles can be "acrylate
functionalized" as described in Bilkadi et al. The sols can also be
matched to the pH of the binder, and can contain counterions or
water-soluble compounds (e.g., sodium aluminate), all as described
in Kang et al. '798.
[0061] The hardcoat can conveniently be prepared by mixing an
aqueous sol of inorganic oxide particles with a free-radically
curable binder precursor (e.g., one or more free-radically curable
monomers, oligomers or polymers that can participate in a
crosslinking reaction upon exposure to a suitable source of curing
energy). The resulting composition usually is dried before it is
applied, in order to remove substantially all of the water. This
drying step is sometimes referred to as "stripping". An organic
solvent can be added to the resulting ceramer composition before it
is applied, in order to impart improved viscosity characteristics
and assist in coating the ceramer composition onto the substrate.
After coating, the ceramer composition can be dried to remove any
added solvent, and then can be at least partially hardened by
exposing the dried composition to a suitable source of energy in
order to bring about at least partial cure of the free-radically
curable binder precursor.
[0062] A variety of binders can be employed in the hardcoat. The
binder is derived from a free-radically polymerizable precursor
that can be photocured once the hardcoat composition has been
coated upon the substrate. Binder precursors such as the protic
group-substituted esters or amides of an acrylic acid described in
'799, or the ethylenically-unsaturated monomers described in '799
et al., are often preferred. Suitable binder precursors include
polyacrylic acid or polymethacrylic acid esters of polyhydric
alcohols, such as diacrylate or di(meth)acrylate esters of diols
including ethyleneglycol, triethyleneglycol,
2,2-dimethyl-1,3-propanediol, 1,3-cyclopentanediol,
1-ethoxy-2,3-propanediol, 2-methyl-2,4-pentanediol,
1,4-cyclohexanediol, 1,6-hexamethylenediol, 1,2-cyclohexanediol,
1,6-cyclohexanedimethanol, resorcinol, pyrocatechol, bisphenol A,
and bis(2-hydroxyethyl) phthalate; triacrylic acid or
trimethacrylic acid esters of triols including glycerin,
1,2,3-propanetrimethanol, 1,2,4-butanetriol, 1,2,5-pentanetriol,
1,3,6,-hexanetriol, 1,5,10-decanetriol, pyrogallol, phloroglucinol,
and 2-phenyl-2,2-methylolethanol; tetraacrylic acid or
tetramethacrylic acid esters of tetraols including
1,2,3,4-butanetetrol, 1,1,2,2,-tetramethylolethane,
1,1,3,3,-tetramethylolpropane, and pentaerythritol tetraacrylate;
pentaacrylic acid or pentamethacrylic acid esters of pentols
including adonitol; hexaacrylic acid or hexamethacrylic acid esters
of hexanols including sorbitol, dipentaerythritol, dihydroxy ethyl
hydantoin; and mixtures thereof. The binder can also be derived
from one or more monofunctional monomers as described in Kang et
al. '798. The binder comprises one or more N,N-disubstituted
acrylamide and or N-substituted-N-vinyl-amide monomers as described
in Bilkadi et al. The hardcoat may be derived from a ceramer
composition containing about 20 to about 80% ethylenically
unsaturated monomers and about 5 to about 40% N,N-disubstituted
acrylamide monomer or N-substituted-N-vinyl-amide monomer, based on
the total weight of the solids in the ceramer composition.
[0063] The inorganic particles, binder and any other ingredients in
the hardcoat are chosen so that the cured hardcoat has a refractive
index close to that of the substrate. This can help reduce the
likelihood of Moire patterns or other visible interference
fringes.
[0064] As mentioned above, the hardcoat can be formed from an
aqueous coating composition that is stripped to remove water prior
to coating, and optionally diluted with a solvent to assist in
coating the composition. Those skilled in the art will appreciate
that selection of a desired solvent and solvent level will depend
on the nature of the individual ingredients in the hardcoat and on
the desired substrate and coating conditions. Kang et al. '798
describes several useful solvents, solvent levels and coating
viscosities.
[0065] The hardcoat can be crosslinked with various agents to
increase the internal cohesive strength or durability of the
hardcoat. Typical crosslinking agents have a relatively large
number of available functional groups, and include tri and
tetra-acrylates, such as pentaerythritol triacrylate and
pentaerythritol tetraacrylate. When used, the crosslinking agent is
often less than about 60 parts, such as about 30 to about 50 parts
by weight per 100 parts by weight of the binder.
[0066] If the hardcoat is prepared by combining an aqueous sol of
colloidal inorganic oxide particles with the binder precursor, then
the sol has a pH such that the particles have a negative surface
charge. For example, if the inorganic particles are predominantly
silica particles, the sol is alkaline with a pH greater than 7,
greater than 8, or greater than 9. The sol may include ammonium
hydroxide or the like so that NH.sup.+.sub.4 is available as a
counter cation for particles having a negative surface charge. If
surface treatment of the colloidal inorganic oxide particles is
desired, a suitable surface treatment agent can be blended into the
sol, e.g., as described in Kang et al. '833, the disclosure of
which is incorporated by reference herein. The free-radically
curable binder precursor is then added to the ceramer composition.
The ceramer composition is stripped to remove substantially all of
the water. For example, removing about 98% of the water, thus
leaving about 2% water in the ceramer composition, has been found
to be suitable. As soon as substantially all of the water is
removed, an organic solvent of the type described in Kang et al.
'798 is typically added in an amount such that the ceramer
composition includes from about 5% to about 99% by weight solids
(about 10 to about 70%).
[0067] The ceramer composition is coated at a coating weight
sufficient to provide a cured hardcoat with a thickness of about 1
to about 100 micrometers, about 2 to about 50 micrometers, or about
3 to about 30 micrometers. After coating, the solvent, if any, is
flashed off with heat, vacuum, and/or the like. The coated ceramer
composition is then cured by irradiation with a suitable form of
energy, such as heat energy, visible light, ultraviolet light or
electron beam radiation. Irradiating with ultraviolet light in
ambient conditions is often utilized due to the relative low cost
and high speed of this curing technique. In addition, the hardcoat
surface optionally is roughened or textured to provide a matte
surface. This can be accomplished in a variety of ways that will be
familiar to those skilled in the art, including embossing the
hardcoat with a suitable tool that has been bead-blasted or
otherwise roughened, by adding a suitable small particle filler
such as silica sand or glass beads to the hardcoat, or by carrying
out cure against a suitable roughened master as described in U.S.
Pat. Nos. 5,175,030 (Lu et al.) and 5,183,597 (Lu).
[0068] The coating composition, reaction product thereof (i.e.
cured coating composition) as well as the protective articles of
the inventions can be used on a variety of display and protective
articles wherein a combination of low surface energy (e.g.
anti-soiling, stain resistance, oil and/or water repellency) and
durability (e.g. abrasion resistance) is desired while also
maintaining optical clarity.
[0069] Various illuminated and non-illuminated display panels are
known. Such displays include multi-character and especially
multi-character, multi-line displays such as liquid crystal
displays ("LCDs"), plasma displays, front and rear projection
displays, cathode ray tubes ("CRTs"), signage, as well as
single-character or binary displays such as light emitting diodes
("LEDs"), signal lamps and switches. The light transmissive (i.e.
exposed) substrate of such display panels may be referred to as a
"lens". The invention is particularly useful for displays having a
viewing surface that is susceptible to damage during normal
use.
[0070] The coating composition, reaction product thereof (i.e.
dried and cured coating composition) as well as the protective
articles of the invention can be employed in a variety of portable
and non-portable information display devices including PDAs, cell
phones (including combination PDA/cell phones), touch-sensitive
screens, wrist watches, car navigation systems, global positioning
systems, depth finders, calculators, electronic books, CD or DVD
players, projection television screens, computer monitors, notebook
computer displays, instrument gauges, instrument panel covers,
signage such as graphic displays (including indoor and outdoor
graphics, and the like), and the like. These devices can have
planar viewing faces, or non-planar viewing faces such as the
slightly curved face of a typical CRT. Typically the display
element is located on or in close physical proximity to a viewing
face of the information display device rather than being spaced an
appreciable distance therefrom.
[0071] The coating composition, reaction product, and protective
article can be employed on a variety of other articles as well such
as for example camera lenses, eyeglass lenses, binocular lenses,
retroreflective sheeting, raised pavement makers (lenses,)
automobile windows, building windows, train windows, boat windows,
aircraft windows, vehicle headlamps and taillights, display cases,
eyeglasses, watercraft hulls, road pavement markings, overhead
projectors, stereo cabinet doors, stereo covers, furniture, floor
finishes, bus station plastic, watch covers, as well as optical and
magneto-optical recording disks, and the like.
[0072] Objects and advantages of this invention are further
illustrated by the following examples, but the particular materials
and amounts thereof recited in these examples, as well as other
conditions and details, should not be construed to unduly limit
this invention.
EXAMPLES
[0073] Test Methods
[0074] 1. Contact Angle--The coatings were rinsed for 1 minute by
hand agitation in IPA before being subjected to measurement of
water and hexadecane contact angles. Measurements were made using
as-received reagent-grade hexadecane (Aldrich) and deionized water
filtered through a filtration system obtained from Millipore
Corporation (Billerica, Mass.), on a video contact angle analyzer
available as product number VCA-2500XE from AST Products
(Billerica, Mass.). Reported values are the averages of
measurements on at least three drops measured on the right and the
left sides of the drops, and are shown in Table 2. Drop volumes
were 5 .mu.L for static measurements and 1-3 .mu.L for advancing
and receding. For hexadecane, only advancing and receding contact
angles are reported because static and advancing values were found
to be nearly equal.
[0075] 2. Durability Test--The abrasion resistance of the cured
films was tested cross-web to the coating direction by use of a
mechanical device capable of oscillating cheesecloth or steel wool
fastened to a stylus (by means of a rubber gasket) across the
film's surface. The stylus oscillated over a 10 cm wide sweep width
at a rate of 3.5 wipes/second wherein a "wipe" is defined as a
single travel of 10 cm. The stylus had a flat, cylindrical geometry
with a diameter of 1.25 inch (3.2 cm) for cheesecloth and a 6 mm
diameter for steel wool. The device was equipped with a platform on
which weights were placed to increase the force exerted by the
stylus normal to the film's surface. The cheesecloth was obtained
from Summers Optical, EMS Packaging, A subdivision of EMS
Acquisition Corp., Hatsfield, Pa. under the trade designation "Mil
Spec CCC-c-440 Product # S12905". The cheesecloth was folded into
12 layers. The steel wool was obtained from Rhodes-American a
division of Homax Products, Bellingham, Wash. under the trade
designation "#0000-Super-Fine" and was used as received. A single
sample was tested for each example, with the weight in grams
applied to the stylus and the number of wipes employed during
testing reported in Tables 3 and 4.
[0076] 3. Bead-Up--An ink marking was applied to the surface layer
with a pen commercially available under the trade designation
"Sanford Sharpie, Fine Point permanent marker, no 30001".
Observations were made to determine whether the ink mark beaded up
when applied to the surface (i.e. "yes" per Table 3 and 4) or did
not bead up (i.e. "no" per Table 3 and 4).
[0077] 4. Ink Repellency--An ink marking was applied to the surface
layer with a pen commercially available under the trade designation
"Sanford Sharpie, Fine Point permanent marker, no 30001".
Observations were made to determine whether the ink mark was easily
removed by wiping with a dry tissue such as commercially available
from Kimberly Clark Corporation, Roswell, Ga. under the trade
designation "SURPASS FACIAL TISSUE". (i.e. "yes" per Table 3 and 4)
or did not bead up (i.e. "no" per Table 3 and 4).
[0078] 5. King Marker Resistance Test--The tip of a KING SIZE
permanent black marker was cut with a razor blade at an angle to
allow for a wide marking width. Using a ruler, a straight line was
drawn on the test sample using the marking at a speed of
approximately 6 inches per second. The marked sample was then
placed next to a 1-5 rating standard with 1 being the lightest and
5 being the darkest. The process was repeated three times and the
average of the three tests was taken.
[0079] 6. Haze and Transmission values of the coated films were
measured by use of BYK Gardner Haze-Clarity-Transmission meter. The
values are reported as percent.
[0080] Ingredients
[0081] As used in the examples, "HFPO-" refers to the end group
wherein a averages about 6.3.
[0082] F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)COOCH.sub.3
wherein a averages about 6.3, with an average molecular weight of
1,211 g/mol, and which can be prepared according to the method
reported in U.S. Pat. No. 3,250,808 (Moore et al.), the disclosure
of which is incorporated herein by reference, with purification by
fractional distillation.
[0083] F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)C(O)F of a
molecular weight of about 1115 can be prepared according to the
method reported in U.S. Pat. No. 3,250,808 (Moore et al), with
purification by fractional distillation
[0084] Trimethylolpropane triacrylate ("TMPTA") was obtained from
Sartomer Company, Exton, Pa. under the trade designation "SR351"
(AC-1)
[0085] Pentaerythritol tetraacrylate was obtained from Sartomer
Company under the trade designation "SR295". (AC-2)
[0086] Triethyleneglycol diacrylate was obtained from Sartomer
Company under the trade designation "SR306". (AC-3)
[0087] The amines: triethylamine, diisopropylethyl amine,
2-amino-2-ethyl-1,3-propane diol, 2-amino-2-methyl-1,3-propane
diol, and 2-amino-1,3-propane diol, 2-aminoethanol,
2-(2-aminoethylamino)ethanol, and 3-amino-1,2-propanediol were
obtained from Sigma-Aldrich, Milwaukee, Wis.
[0088] Acryloyl chloride was obtained from Sigma-Aldrich.
[0089] .omega.-hydro 2,2,3,3,4,4,5,5-octafluoropentyl acrylate
(H--C.sub.4F.sub.8--CH.sub.2O--C(O)--CH.dbd.CH.sub.2) was obtained
from Oakwood Products, West Columbia, S.C. (MP-2)
[0090] The UV photoinitiator used was obtained from Ciba Specialty
Products, Terrytown, N.Y. under the trade designation "Darocur
1173".
[0091] Preparation of HFPO--C(O)--NH--CH.sub.2CH.sub.2--OH Starting
Material (i.e. HFPO-AE-OH)
[0092] 50.0 g of the HFPO--C(O)OCH.sub.3 (i.e. Mw=1211 g/mole) was
placed in 200 ml round bottom flask. The flask was purged with
nitrogen and placed in a water bath to maintain a temperature of
50.degree. C. or less. To this flask was added 3.0 g (0.045 mol) of
2-aminoethanol. The reaction mixture was stirred for about 1 hr,
after which time an infrared spectrum of the reaction mixture
showed complete loss of the methyl ester band at 1790 cm.sup.-1 and
the presence of the strong amide carbonyl stretch at 1710
cm.sup.-1. 200 ml of methyl t-butyl ether (MTBE) was added to the
reaction mixture and the organic phase was extracted twice with
water/HCl (.about.5%) to remove unreacted amine and methanol. The
MTBE layer was dried with MgSO.sub.4. The MTBE was removed under
reduced pressure to yield a clear, viscous liquid. .sup.1H Nuclear
magnetic resonance spectroscopy (NMR) and infrared spectroscopy
(IR) confirmed the formation of the above-identified compound.
[0093] Preparation of Monofunctional Perfluoropolyether Acrylate
(MP-1)
[0094] HFPO--C(O)N(H)CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2
(HFPO-AEA)
[0095] HFPO-AE-OH (600 g) was combined with ethyl acetate (600 g)
and triethylamine (57.9 g) in a 3-neck round bottom flask that was
fitted with a mechanical stirrer, a reflux condenser, addition
funnel, and a hose adapter that was connected to a source of
nitrogen gas. The mixture was stirred under a nitrogen atmosphere
and was heated to 40.degree. C. Acryloyl chloride (51.75 g obtained
from Aldrich Chemical) was added dropwise to the flask from the
addition funnel over about 30 minutes. The mixture was stirred at
40.degree. C. overnight. The mixture was then allowed to cool to
room temperature, diluted with 300 mL of 2N aqueous HCl and
transferred to a separatory funnel. The aqueous layer was removed
and the ethyl acetate layer was extracted with another 300 ml
portion of 2N HCl. The organic phase was then extracted once with 5
wt-% aqueous NaHCO.sub.3 separated, dried over MgSO.sub.4 and
filtered. Removal of the volatile components using a rotary
evaporator resulted in 596 g of product (93% yield). .sup.1H NMR
and IR spectroscopy confirmed the formation of the above-identified
compound.
[0096] Synthesis of Perfluoropolyether Polyacrylate Compounds
[0097] 1. Preparation of
HFPO--C(O)N(H)C(CH.sub.2OH).sub.2CH.sub.2CH.sub.3 Starting
Material
[0098] To a 500 ml 3 necked flask equipped with a stir bar and
reflux condenser was charged 11.91 g (0.1 mol)
H.sub.2NC(CH.sub.2OH).sub.2CH.sub- .2CH.sub.3 and 60 g THF. Next
via dropping funnel was added 121.1 g (0.1 mol) HFPO--C(O)OCH.sub.3
over about 80 min at a bath temperature of about 85.degree. C. The
reaction was cloudy at first, but became clear about 1 h into the
reaction. After addition was complete, the heating bath was shut
off and the reaction was allowed to cool over the weekend. The
material was concentrated at 55.degree. C. under aspirator vacuum
to yield 130.03 g of a light colored syrup. NMR analysis showed the
product to be an 87:13 mixture of the structures I to II as
follows: 3
[0099] Preparation of Polyfunctional Perfluoropolyether
Acrylate
[0100]
HFPO--C(O)N(H)C(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2CH.sub.2CH.sub.3
(FC-1)
[0101] To a 250 ml 3 necked round bottom flask equipped with
overhead stirrer was charged 65 g (0.05 mol) of
HFPO--C(O)N(H)C(CH.sub.2OH).sub.2C- H.sub.2CH.sub.3, the product
mixture generated above, 12.65 g (0.125 mol) triethylamine and 65 g
ethyl acetate. To the flask at room temperature was added 11.31
g(0.125 mol) acryloyl chloride using a pressure-equalizing dropping
funnel over 12 min, with the reaction temperature rising from 25 to
a maximum of 40.degree. C. The dropping funnel was rinsed with 5 g
additional ethyl acetate that was added to the reaction that was
then placed in a 40.degree. C. bath and allowed to react for 2
hours and 10 min additional time. The organic layer was then
successively washed with 65 g 2% aqueous sulfuric acid, 65 g 2%
aqueous sodium bicarbonate, and 65 g water, dried over anhydrous
magnesium sulfate, filtered, treated with 16 mg methoxyhydroquinone
(MEHQ), and concentrated on a rotary evaporator at 45.degree. C. to
yield 62.8 g of crude product. Next 35 g of this material was
chromatographed on 600 ml of silica gel (SX0143U-3, Grade 62,
60-200 mesh, EM Science) using 25:75 ethyl acetate: heptane as an
eluent. The first two fractions were 250 ml in volume, the
remaining fractions were 125 ml in volume. Fractions 4-10 were
combined, 8 mg MEHQ was added to the fractions, which were
concentrated on a rotary evaporator at 55C to provide 25.36 g of
product that was analyzed by NMR, and found to be an 88:12 mixture
of the structures III to IV. 4
[0102] 2. Preparation of HFPO--C(O)N(H)C(CH.sub.2OH).sub.2H
Starting Material
[0103] By a method similar to the preparation of
HFPO--C(O)N(H)C(CH.sub.2O- H).sub.2CH.sub.2CH.sub.3, 106.74 g
(0.088 mol) HFPO--C(O)CH.sub.3 was reacted with 8.03 g (0.088 mol)
2-amino-1,3-propanediol in 51 g THF to provide a product that was
93:7 amide diol: ester amino-alcohol.
[0104] Preparation of Polyfunctional Perfluoropolyether
Acrylate
[0105]
HFPO--C(O)N(H)C(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2H(FC-2)
[0106] In a method similar to the preparation of
HFPO--C(O)N(H)C(CH.sub.2O-
C(O)CH.dbd.CH.sub.2).sub.2CH.sub.2CH.sub.3, 50 g (0.3936 mol)
HFPO--C(O)N(H)C(CH.sub.2OH).sub.2H Starting Material was reacted
with 8.55 g (0.0945 mol) acryloyl chloride and 9.56 g (0.946 mol)
triethylamine in 100 g of ethyl acetate, to provide after workup
and chromatography, the 93:7 mixture of diacrylate and
acrylamide-acrylate.
[0107] 3. Preparation of
HFPO--C(O)N(H)CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2O- H Starting
Material
[0108] A 100 ml round bottom flask was charged with 50.0 g (0.413
mol) HFPO--C(O)OCH.sub.3 and heated to 40C in an oil bath. The
flask was removed from the bath and 4.30 (0.413 mol)
2-(2-aminoethylamino)ethanol was charged to the flask. The contents
were swirled together and heated with stirring at 65.degree. C. in
an oil bath for 3 h, then concentrated at 65.degree. C. on a rotary
evaporator under aspirator pressure to provide the product.
[0109] Preparation of Polyfunctional Perfluoropolyether
Acrylate
[0110]
HFPO--C(O)N(H)CH.sub.2CH.sub.2N(C(O)CH.dbd.CH.sub.2)CH.sub.2CH.sub.-
2OC(O)CH.dbd.CH.sub.2 (FC-3)
[0111] In a method similar to the preparation of
HFPO--C(O)N(H)C(CH.sub.2O-
C(O)CH.dbd.CH.sub.2).sub.2CH.sub.2CH.sub.3, 64.15 g (0.050 mol)
HFPO--C(O)N(H)CH2CHNHCH2CH.sub.2OH was reacted with 11.26 g (0.125
mol) acryloyl chloride and 12.65 g (0.125 mol) triethylamine in 65
g of ethyl acetate, to provide after workup and chromatography, the
desired product.
[0112] 4. Preparation of HFPO--C(O)N(H)CH.sub.2CH(OH)CH.sub.2OH
Starting Material
[0113] By a method similar to the preparation of
HFPO--C(O)N(H)C(CH.sub.2O- H).sub.2CH.sub.2CH.sub.3, 121.1 g (0.100
mol) HFPO--C(O)CH.sub.3 was reacted with 9.11 g (0.100 mol)
1-amino-2,3-propanediol in 55.7 g THF to provide a product that was
86:14 amide diol: ester amino-alcohol.
[0114] Preparation of Polyfunctional Perfluoropolyether Acrylate
(FC-4)
[0115]
HFPO--C(O)N(H)CH.sub.2CH(OC(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)CH.dbd.C-
H.sub.2
[0116] In a method similar to the preparation of
HFPO--C(O)N(H)C(CH.sub.2O-
C(O)CH.dbd.CH.sub.2).sub.2CH.sub.2CH.sub.3, 63.5 g (0.050 mol)
HFPO--C(O)N(H)CH.sub.2CH(OH)CH.sub.2OH was reacted with 11.26 g
(0.0945 mol) acryloyl chloride and 9.56 g (0.946 mol) triethylamine
in 100 g of ethyl acetate, to provide after workup and
chromatography, the 86:14 mixture of diacrylate and
acrylamide-acrylate.
[0117] 5. Preparation of
HFPO--C(O)--NH--C(CH.sub.3)(CH.sub.2--OH).sub.2 Starting
Material
[0118] 2-amino-2-methyl 1,3-propane diol (2.8 g, 0.027 mol,
commercially available from Aldrich) was charged to a 200 ml round
bottom flask and purged with nitrogen. The amine was dissolved in
40 g of 3:1 by weight mixture of methyl t-butyl ether and methanol
and heated to reflux. After the amine was dissolved fully,
oligomeric HFPO methyl ester (HFPO--C(O)OCH.sub.3, 25.0 g, 0.021
mol, Mw=1211 g/mole) was added to the solution and the reaction was
allowed to progress for approximately 24 hrs. The reaction mixture
was analyzed by IR spectroscopy. The spectrum showed the presence
of an amide signal at 1717 cm.sup.-1 and the absence of the methyl
ester signal at 1790 cm.sup.-1. The reaction mixture was worked up
by the addition of 250 ml of water/HCl (15 wt %), followed by
extraction and further addition of methyl T-butyl ether. CaCl.sub.2
was used to enhance the phase split between the organic and aqueous
phases. The MTBE layers were combined and dried with MgSO.sub.4.
The MTBE was removed under reduced pressure to yield a clear,
viscous liquid. Further drying at 0.1 mmHg and RT for 16 hrs,
resulted in 23.1 g (85% yield). .sup.1H NMR and IR spectroscopy
confirmed the formation of the above-identified compound.
[0119] Preparation of Polyfunctional Perfluoropolyether
Acrylate
[0120] HFPO--C(O)N(H)C(CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2CH.sub.3
(FC-5)
[0121] To a 100 ml 3 necked round bottom flask equipped with
magnetic stir bar, thermometer, condenser and addition funnel was
charged 15 g (0.011 mol) of
HFPO--C(O)N(H)C(CH.sub.2OH).sub.2CH.sub.3, the product mixture
generated above, 2.97 g (0.023 mol) N,N-diisopropylethylamine and
25 g ethyl acetate. The flask was heated to 40.degree. C. To the
flask was added 2.08 g (0.023 mol) acryloyl chloride dropwise over
about 10 minutes. The dropping funnel was rinsed with 5 g
additional ethyl acetate that was added to the reaction. The
reaction was allowed to run overnight at 40.degree. C. The organic
layer was then cooled and successively washed twice with 25 g 2N
hydrochloric acid, twice with 25 g 5% aqueous sodium bicarbonate,
and 25 g water, dried over anhydrous magnesium sulfate, filtered
and dried on a rotary evaporator at 50.degree. C. to yield 10.14 g
product.
[0122] 6. Preparation of
HFPO--C(O)NH(C.sub.2H.sub.4NH).sub.5C(O)--HFPO:
[0123] In a sealed 120 mL Pyrex tube, 20 g of HFPO--CO.sub.2Me (20
mmol) was mixed with 2.32 g NH.sub.2(C.sub.2H.sub.4NH).sub.5H (10
mmol), and reacted at 110.degree. C. for 4 hours with magnetic
stirring. In less than 20 minutes, the mixture was turned into a
clear homogenous solution. The solution was allowed to react for 5
hours. From FTIR analysis, the signal at 1787 cm.sup.-1
(--CO.sub.2Me) was disappeared, and showed the corresponding amide
linkage at 1718 cm.sup.-1. After methanol strip under full vacuum,
gave the corresponding perfluoroether amine oligomer with MW
.about.2626.38.
[0124] 7. Preparation of
HFPO--C(O)NH(C.sub.2H.sub.4NH).sub.5C(O)--HFPO/IE- M in 1/2 ratio:
5
[0125] R.sub.3 is independently H or
CH.sub.2.dbd.C(CH.sub.3)C(O)--OC.sub.- 2H.sub.4NHC(O)-- in 1/1
ratio
[0126] In a 100 mL flask, charged with 5.96 g
HFPO--C(O)NH(C.sub.2H.sub.4N- H).sub.5--C(O)--HFPO (2.27 mmol), 5.0
g HFE-7100 and 15 g EtOAc. To above clear solution, added 0.73 g
(4.7 mmol) IEM in 5 g EtOAc at room temperature. An exothermic
reaction started, and the solution turned into cloudy. After
continued reaction for 0.5 hour, the solvent was stripped, and the
residue was dissolved in acetone. From NMR, 1714.16 cm.sup.-1 and
1637.20 cm.sup.-1 were observed for the corresponding --CONH-- and
CH.sub.2.dbd.CMe-, but no --NCO signal.
[0127] 8. Preparation of
HFPO--C(O)NH(C.sub.2H.sub.4NH).sub.5C(O)--HFPO/Gl- ycidyl
methacrylate in 1/4 ratio: 6
[0128] In a 100 mL flask, charged with 13.43 g
HFPO--C(O)NH(C.sub.2H.sub.4- NH).sub.5C(O)--HFPO (5.11 mmol).
Glycidyl methacrylate (MW=142.15, 2.88 g, 20.26 mmol) was added,
and the mixture was reacted at 70C for 2 hours to form a wax solid,
which is soluble in IPA.
[0129] Preparation of the Coating Solutions:
[0130] Substrates were coated with polymerizable compositions using
materials and amounts by weight as reported in Table 1. All
polymerizable components were diluted to 10 percent by weight total
solids in methyl ethyl ketone. Two percent by weight of
photoinitiators PI-1 was included in the polymerizable compositions
using a 10 percent solids photoinitiator solutions in methyl ethyl
ketone. The photoinitiator was added before dilution to the final
percent by weight total solids. Dilution to the final percent by
weight total solids was achieved using methyl isobutyl ketone
[0131] Coating, Drying, Curing Process
[0132] Two different substrates, each having a hardcoat surface
layer were used in the Examples. The first substrate (S-1) was
prepared from a transparent polyethylene terephthalate (PET) film
obtained from e.i. DuPont de Nemours and Company, Wilmington, Del.
under the trade designation "Melinex 618" having a thickness of 5.0
mils and a primed surface. A hardcoat composition that was
substantially the same as Example 3 of U.S. Pat. No. 6,299,799 was
coated onto the primed surface and cured in a UV chamber having
less than 50 parts per million (ppm) oxygen. The UV chamber was
equipped with a 600 watt H-type bulb from Fusion UV systems,
Gaithersburg Md., operating at full power. The second substrate
(S-2) was a matte film having a preapplied hardcoat surface layer
commercially available from U.S.A. Kimoto Tech, Cedartown, Ga.
under the trade designation "N4D2A" (S-2). The matte film was used
without further modification.
[0133] The hardcoat was applied to the Melinex 618 film with a
metered, precision die coating process. The hardcoat was diluted in
IPA to 30 wt-% solids and coated onto the 5-mil PET backing to
achieve a dry thickness of 5 microns. A flow meter was used to
monitor and set the flow rate of the material from a pressurized
container. The flow rate was adjusted by changing the air pressure
inside the sealed container which forces liquid out through a tube,
through a filter, the flow meter and then through the die. The
dried and cured film was wound on a take up roll and used as the
input backing for the coating solutions described below.
[0134] The hardcoat coating and drying parameters for S-1 were as
follows:
[0135] Coating width: 6" (15 cm)
[0136] Web Speed: 30 feet (9.1 m) per minute
[0137] Solution % Solids: 30.2%
[0138] Filter: 2.5 micron absolute
[0139] Pressure Pot: 1.5 gallon capacity (5.71)
[0140] Flow rate: 35 g/min
[0141] Wet Coating Thickness: 24.9 microns
[0142] Dry Coating Thickness: 4.9 microns
[0143] Conventional Oven Temps:
[0144] 140.degree. F. (60.degree. C.) Zone 1
[0145] 160.degree. F. (53.degree. C.) Zone 2
[0146] 180.degree. F. (82.degree. C.) Zone 3
[0147] Length of oven 10 feet (3 m)
[0148] The coating compositions of the invention were coated onto
the hardcoat layer of either S-1 or S-2 using a precision, metered
die coater. For this step, a syringe pump was used to meter the
solution into the die. The solutions were diluted to a
concentration of 2-2.5% methylethyl ketone and coated onto the
hardcoat layer to achieve a dry thickness of 40-60 nm. The material
was dried in a conventional air flotation oven and then sent
through the UV chamber having less than 50 ppm oxygen. The UV
chamber was equipped with a 600 watt H-type bulb from Fusion UV
systems, Gaithersburg Md., operating at full power.
[0149] The surface layer coating and drying parameters were as
follows:
[0150] Coating width: 4" (10 cm)
[0151] Web Speed: 10 feet per minute
[0152] Solution % Solids: 2.0-2.5%
[0153] Pump: 60 cc Syringe Pump
[0154] Flow rate: 1.2 cc/min
[0155] Wet Coating Thickness: 4.1 microns
[0156] Dry Coating Thickness: 60 nm
[0157] Conventional Oven Temps:
[0158] 65.degree. C. Zone 1
[0159] 65.degree. C. Zone 2
[0160] Length of oven 10 feet (3 m)
1TABLE 1 Coating Formulations Example (AC-1) (MP-1) (FC-1) (FC-2)
Other Substrate 9a 95 5 S-1 9b 95 5 S-2 10b 20 70 10 S-2 11b 20 10
70 S-2 12a 95 5 S-1 12b 95 5 S-2 13a 97.5 2.5 S-2 14a 98.75 1.25
S-2 15b 95 5 95 (AC-2) S-2 16b 95 5 S-2 17a 90 5 5 (MP-2) S-1 19a
85 5 10 (FC-3) S-1 20a 95 5 FC-3 S-1 A 95 5 FC-4 S-1 Compar- 100
ative A Compar- 100 ative B
[0161]
2TABLE 2 Test Results Contact angle Contact Angle Haze Trans with
water with Hexadecane before before Example Static Advancing
Receding Advancing Receding testing testing 9a 108 118 97 65 59
0.54 95 10b 110 123 89 70 60 NM NM 11b 110 123 89 69 59 NM NM 12a
106 119 96 65 57 0.46 94 13a 94 109 85 52 44 0.52 93.4 14a 55 73 42
NM NM 0.23 93.1 15b 105 119 94 66 59 NM NM 16b 108 121 86 67 59 NM
NM 17a 104 118 89 65 56 0.37 92.5 18a 108 119 98 66 56 0.37 91.9
19a 107 120 97 67 56 0.37 92.1 20a 107 120 95 68 57 0.39 92.2
Comparative 59 76 47 18 NM NM NM A NM--(Not Measured)
[0162]
3TABLE 3 Cheesecloth Durability Test Results Before cheesecloth
After rubs Cheesecloth rubs Ex- Wt, in g Ink re- Ink Ink Ink am-
Applied No. of pellency Beads Up repellency Beads Up ple to Stylus
Cycles Yes/No Yes/No Yes/No Yes/No 16b 725 200 Y Y Y Y 12b 725 200
Y Y Y Y Com- 725 200 N N N N par- ative B
[0163]
4TABLE 4 Steel Wool Durability Test Results Before Steel After
Steel Wt, in g Wool rubs Wool rubs Ex- Applied Ink Ink Ink Ink am-
to No. of repellency Beads Up repellency Beads Up ple Stylus Cycles
Yes/No Yes/No Yes/No Yes/No 9a 200 500 Y Y Y Y 12a 200 500 Y Y Y Y
17a 1000 750 Y Y Y Y 18a 1000 750 Y Y Y Y 19a 1000 500 Y Y Y Y 20a
1000 500 Y Y Y Y Com- 200 500 N N N N par- ative B
[0164] Hardcoat Compositions
[0165] In another example (Ex. 21), an embodied perfluoropolyether
poly(meth)acryl compound was an ingredient of the hardcoat
formulation. A curable liquid ceramer composition was prepared by
dilution in a small glass vial of 0.02 g FC-5 with 25 g of a
hardcoat composition that is substantially the same as Example 3 of
U.S. Pat. No. 6,299,799 ("S-1"). The mixture was mixed well then
diluted by weighing 1 gram of the fluorine-containing hardcoat
formula into a vial and diluting with 7.0 g hardcoat. The resulting
mixture was coated onto PET film using a #30 wire wound bar. The
uncured mixture was dried at room temperature for 5 minutes,
followed by 5 minutes at 60.degree. C., then UV cured with one pass
through the UV chamber.
[0166] Test Result:
[0167] The UV cured hardcoat containing the perfluoroether
diacrylate showed ink repellency.
[0168] 22. Preparation of
[0169]
CH.sub.2.dbd.CHCO(O)CH.sub.2CH(OC(O)Rf)CH.sub.2OCH.sub.2CH(OR)CH.su-
b.2OCH.sub.2CH(OCORf)CH.sub.2.degree. C. (O)CH.dbd.CH.sub.2 where
Rf is HFPO MW1115 and the central OR is a mixture of OH and OCORf.
(HFPO3-DGDA)
[0170] A mixture of 3.5 g (0.01 mol) glycerol 1,3-diglycerolate
diacrylate (Aldrich), 4.0 g diisopropylethylamine, and 100 ml
CH.sub.2Cl.sub.2 was treated with 35.5 g
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)C(O)F of a molecular
weight of about 1115 and stirred as a heterogeneous mixture for 3
hr. The mixture was washed twice with about 50 ml water, dried over
MgSO.sub.4, and stripped to 29.3 g pale yellow oil, n.sub.D 1.3553
(21.1C). 2D-nmr showed a complex mixture with about 2.9 HFPO chains
per 2 acrylates, but some secondary OH was present as well as some
COOH and some of the acrylates were secondary, instead of primary
as the Aldrich structure is assigned.
[0171] 23. A UV-curable hardcoat solution was prepared with 0.4 phr
HFPO3-DGDA in a curable liquid ceramer composition. The ceramer
hardcoat was prepared by adding 0.2078 grams of the fluorochemical
modifier and 0.20 g H(CF.sub.2).sub.4CH.sub.2OH to 100 grams of 50%
solids hardcoat composition that is substantially the same as
Example 3 of U.S. Pat. No. 6,299,799 ("S-1"). The mixture was
coated using a #8 wire wound onto a polyester film substrate
commercially available from Mitsubishi under the trade designation
"Hostaphan.RTM. 4507". The coated film was air dried 5 minutes,
followed by oven heating 5 minutes at 70.degree. C., then UV curing
with one pass through the processor.
[0172] Test Result:
[0173] A clear film was produced that exhibit ink repellency and
wipes clean. Static water contact angle was 100 degrees, and static
hexadecane contact angle was 65 degrees.
[0174] Coating on Vinyl Sheet
[0175] Preparation of HFPO dihydroalcohol,
F-[CF(CF.sub.3)CF.sub.2O].sub.a- CF(CF.sub.3)CH.sub.2OH, a=5-7
[0176] A 3-L round bottom flask equipped with a mechanical stirrer
and nitrogen bubbler was charged with 1 liter of glyme, sodium
borohydride (85 g, 2.2 mol) and heated to 77.degree. C. Oligomeric
HFPO ester, F-[CF(CF.sub.3)O].sub.aCF(CF.sub.3)COOCH.sub.3, a=5-7
(810 g, 0.8 mol) prepared as described in U.S. Pat. No. 3,114,778
was added to the stirred slurry over one hour. An exotherm was
observed and heated to 88.degree. C. for 18 hours. Heat was removed
and 300 g methanol was added over three hours with evolution of
hydrogen. Reaction was quenched with a mixture of 290 g of
concentrated sulfuric acid in 1 kg of water. Solvents were removed
by heating to a final head temperature of 93.degree. C.
Fluorochemical lower phase was separated and vacuum heated to
remove water. Oligomer HFPO dihydroalcohol,
F-[CF(CF.sub.3)O].sub.aCF(CF.sub.3)C- H.sub.2OH, a=5-7 (688 g, 0.7
mol) was made in an 88% yield and the structure was confirmed by
FTIR and H and FNMR.
[0177] 25. Preparation of Oligomeric HFPO dihydroglycidol
diacrylate
F-[CF(CF.sub.3)CF.sub.2O].sub.aCF(CF.sub.3)CH.sub.2OCH.sub.2CH(OC(O)CH.db-
d.CH.sub.2)CH.sub.2OC(O)CH.dbd.CH.sub.2, a=5-7
[0178] To a 500 ml 3-neck round bottom flask equipped with a
mechanical stirrer and nitrogen bubbler was charged with oligomeric
HFPO dihydroalcohol (200 g, 0.2 mol) made as just described and
sodium methoxide 25% in methanol (43 g, 0.2 mol) and heated to
95.degree. C. After one hour, methanol along with volatiles were
stripped and cooled to 45.degree. C. Glycidol (15 g, 0.2 mol) was
added and the flask was heated to 100.degree. C. for 18 hours.
Reactor was cooled to 25.degree. C. and 200 g CFCl.sub.2CF.sub.2Cl
solvent was added along with 25 ml of a 10% sulfuric acid solution.
Mixture was water washed and the fluorochemical phased was dried
with MgSO.sub.4, filtered and vacuum dried to yield oligomer HFPO
dihydroglycidol (131 g, 0.62 mol) for a 62% yield and confirmed by
H and FNMR. To a 250 ml round bottom flask equipped with mechanical
stirrer and nitrogen bubbler was charged with oligomer HFPO
dihydroglycidol (30 g, 0.2 mol), 50 g glyme and 5 g triethylamine.
One phase was obtained by addition of 18 g CFCl.sub.2CF.sub.2Cl
solvent and heated to 45.degree. C. for thirty minutes. Addition of
acryloyl chloride (4.6 g, 0.05 mol) over thirty minutes with an
exotherm and precipitate formation. Added 63 g water and the lower
fluorochemical phase was dried with MgSO.sub.4, filtered and
stripped dry under vacuum. A yield of 65% oligomeric HFPO
dihydroglycidol diacrylate F-[CF(CF.sub.3)
CF.sub.2O].sub.aCF(CF.sub.3)CF.sub.2CH.sub.2OCH.sub.2CH(OC(O)CH.dbd.CH.su-
b.2)CH.sub.2OC(O)CH.dbd.CH.sub.2, a=5-7 was confirmed by H and
FNMR.
[0179] 24 and 25. Preparation of Coating Composition
[0180] 0.025 g of
C.sub.3F.sub.7O--[CF(CF.sub.3)CF.sub.2O].sub.aCF(CF.sub.-
3)CH.sub.2OCH.sub.2CH(OC(O)CH.dbd.CH.sub.2)CH.sub.2OC(O)CH.dbd.CH.sub.2,
a=4-6 (prepared as just described) was added to 9.975 g of an
aliphatic acrylate commercially available from Sartomer under the
trade designation "Sartomer 306". Example 25 was prepared in the
same manner except that a 9:1 blend of "Sartomer 306 and "Sartomer
492" were employed. 0.05 g of "Darocur 1173" photoinitiator was
added to each of Examples 24 and 25. The three materials were mixed
together in a vial and placed on a shaker for 5 minutes before
coating. Each sample was then coated onto a piece of white soft
vinyl (4".times.6") obtained from Armstrong, Lancaster, Pa.,
Excelon. The samples were hand coated using # 10 Meyer bar then
photo-polymerized using a PRC UV processor (Model # 84-502) at a
line speed of 30 ft/min. This gave a shiny smooth hard coat.
[0181] The two treated vinyl samples were then tested for ink
repellency and receding contact angle. Examples 24 and 25 had
hexadecane receding contact angles of 62 and 48 respectively and
the King Size Permanent Marker Resistance of both samples was
"1".
* * * * *